Exuded transition metal films on glass-ceramic articles

ABSTRACT

Suitable glass-ceramic base compositions, including some silicates, aluminosilicates, lithium aluminosilicates, and boroaluminates, are modified by the addition of suitable quantities of transition metal oxides prior to melting and forming into thermally-crystallizable glass articles. Appropriate crystallization and post-crystallization heat treatments are thereafter employed to cause crystallization of the articles and the formation and growth of films thereon, which films are characterized by the presence of transition metal compounds, typically of spinel structure, therein. Such films demonstrate useful electrical, magnetic, catalytic and/or light-absorptive properties.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of my copending application, Ser. No. 431,148, filed Jan. 1, 1974, and commonly assigned herewith, now U.S. Pat. No. 3,962,514.

BACKGROUND OF THE INVENTION

Transition-metal-containing crystalline compounds of spinel structure are important constituents of inorganic coatings employed for an extremely wide variety of applications. For example, iron-containing spinels such as magnetite (Fe₃ 0₄), and also other ferrites such as manganese, cobalt and nickel ferrites, have been applied to a variety of organic and inorganic substrates in order to impart desirable electromagnetic properties thereto. Processes for applying such coatings and controlling the properties thereof in the course of deposition comprise a large body of technology and include vapor deposition, precipitation, evaporation and thermal decomposition techniques.

Similarly, a large number of transition metal oxides of spinel or ilmenite structure are included within the classes of catalytically-active compounds, and have been applied in the form of coatings to a variety of metal, glass and ceramic supports for use in catalytic processes. Among the transition metal oxides useful in catalysis are Mn₃ O₄, MnAl₂ O₄, MnCr₂ O₄, FeAl₂ O₄, CoAl₂ O₄, NiAl₂ O₄, CoTiO₃, MnTiO₃, FeTiO₃, CeTiO₄, CuAl₂ O₄ and CuCr₂ O₄.

In virtually all applications wherein transition metal oxide coatings are employed in combination with inorganic substrates, coating adherence and durability are extremely important properties. In many applications, binders are required to enable these coatings to demonstrate the toughness needed to withstand the shocks and abrasion of use. In the case of inorganic substrates exhibiting low surface porosity, bonding agents or high sintering temperatures are required to obtain coatings demonstrating a useful degree of adherence to the support. In the case of magnetic recording media such as magnetic memory discs, extreme surface flatness is required, compounding the difficulty of providing a durable, adherent coating.

In catalytic applications, particularly where high temperatures are involved, interactions between active oxide coatings and incompatible binders and/or supporting materials can cause reductions in activity due to the growth of inactive reaction phases or sintering. Yet the attainment of good adherence to commercial supports often requires the use of binders and/or high-temperature sintering treatments.

What is therefore desired is a means for providing transition-metal-containing oxide surface layers on compatible inorganic supports wherein bonding agents, binders, and high sintering temperatures are not required to obtain adherence, toughness and stability in the active film.

SUMMARY OF THE INVENTION

I have now devised a means of providing transition metal oxide surface films on glass-ceramic articles which overcomes the various problems of adherence, flatness, durability and thermal stability encountered in the prior art. Glass-ceramic articles are a relatively recent development in ceramic technology, the first commercially practicable articles being described by Stookey in U.S. Pat. No. 2,920,971. Briefly, the manufacture of glass-ceramics conventionally involves first compounding and melting a batch for a glass to which an amount of a crystallization-promoting or nucleating agent has been added, thereafter forming a glass article from the melt and cooling the article at least below the transformation range of the glass, and finally reheating the glass article according to a defined time-temperature schedule to produce internal nucleation and crystallization in situ thereof. The resulting article is uniformly crystallized, non-porous, free of voids, and retains the shape of the parent glass article. For a more complete description of glass-ceramic manufacturing theory and practice, reference may be made to the aforementioned Stookey patent and numerous subsequently published patents, articles and texts.

The present invention is based on the discovery that certain base glass-ceramic compositions, when modified by the addition of specified quantities of transition metal oxide modifiers, can be crystallized and thereafter heat-treated in a manner which will promote the formation and growth of transition metal oxide surface films thereon. In this way, glass-ceramic articles having integral surface films demonstrating desirable electrical, magnetic, light-absorptive and/or catalytic properties may be produced. The integral nature of these so-called exuded transition metal oxide films inherently provides the desired properties of adherence, durability and substrate compatibility.

Transition metals suitable for inclusion in glass-ceramic base compositions according to the invention include manganese, iron, cobalt, copper, chromium, nickel and vanadium. Among the useful crystalline phases which may be present in exuded transition metal oxide films produced according to the invention are Mn₃ O₄, Co₃ O₄, NiFe₂ O₄, MnFe₂ 0₄, CoFe₂ O₄, CuCr₂ O₄, FeCr₂ O₄, MnCr₂ 0₄, CoMn₂ 0₄, CoTiO₃, Co₂ TiO₄, MnTiO₃, FeTiO₃, VAlO₄, CuAl₂ O₄, CrAl₂ 0₄, NiAl₂ 0₄, FeAl₂ 0₄, CoAl₂ 0₄, MnAl₂ O₄, Mn₂ Al₂ (SiO₄)₂, MnNb₂ 0₆, NiNb₂ 0₆ and Ti₂ Nb₁₀ 0₂₉.

In many cases, exuded transition-metal-containing films produced according to the invention also demonstrate useful light reflecting and transmitting properties. Decorative films over a wide range of colors may be produced, or transparent or translucent bodies exhibiting sharp electromagnetic cutoff values may result.

The end properties of the particular film produced depends on the composition of the base glass-ceramic composition selected as a support and upon the transition metal oxide additives selected for incorporation into the base composition.

Whereas certain of the base glass-ceramic compositions amenable to treatment according to the present invention are generally known, the capability of producing useful exuded transition-metal-containing films on glass-ceramics had been found to depend not only upon the composition of the glass-ceramic material selected as a base but also upon the nature of the subsequent treatment of the material to cause the formation and growth of useful exuded oxide films thereon. In general, the formation and growth of transition-metal-containing oxide films is promoted by heat-treating transition metal-doped glass-ceramic articles under reducing conditions at elevated temperatures for a period of time sufficient to attain the desired degree of film growth.

There is some evidence that the initiation of film formation occurs in some systems in the course of crystallization in situ of the glass precursor body. While such films are not typically sufficiently developed to be useful, the existence of the phenomenon indicates that crystallization need not be entirely complete prior to the commencement of the reduction heat treatment which is employed to achieve the growth of the exuded film. However, completion of the bulk crystallization process prior to or at least concurrently with the formation of the exuded transition-metal-containing film is normally required.

For the purposes of the present description, exuded transition-metal-containing films include not only films composed essentially entirely of transition metal oxide compounds such as MnAl₂ O₄, Fe₃ O₄, and the like, but also films wherein such compounds are in solid solution or combination with other crystalline species such as transition-metal-free aluminates, silicates, titanates, or similar compounds. Glassy matrix phases commonly found in semi-crystalline glass-ceramic materials produced from the crystallization in situ of glasses may also be present in these exuded films. In the preferred embodiments, however, crystalline transition metal oxide compounds normally comprise a predominate proportion (at least about 50% by volume) of the exuded film.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

A particularly useful class of base glass-ceramic compositions suitable for treatment according to the invention are the aluminosilicate and lithium aluminosilicate compositions characterized by the presence of beta-spodumene and/or beta quartz solid solutions as principal crystal phases. This base glass composition area includes compositions consisting essentially, in weight percent on the oxide basis as calculated from the batch, of about 55-80% SiO₂, 14-35% Al₂ O₃, 0-5% Li₂ O, 0-7% TiO₂, 0-10% ZrO₂, 3-13% total of TiO₂ + ZrO₂, and 0-3% F, to which may be added a total of 0.1-10% of transition metal oxide additives. Suitable transition metal oxide additives include one or more oxides selected in the indicated proportions from the group consisting of 0-5% MnO₂, 0-5% Fe₂ O₃, 0-3% CoO, 0-2% CuO, 0-2% Cr₂ O₃, 0-3% V₂ O₅, and 0-10% NiO. Minor amounts of other compounds may, of course, be included within these compositions as aids in melting, to modify properties, or for other known purposes. Examples of additives which have been employed are La₂ O₃, Nb₂ O₅, BaO, B₂ O₃, P₂ O₅, MgO, CaO, ZnO, Na₂ O, K₂ O, Ta₂ O₅, Cl, Br, As₂ O₃, and Sb₂ O₃. The total amount of these additives, however, is generally held to not more than about 10% by weight, so that the basic constituents SiO₂, Al₂ O₃, Li₂ O, TiO₂, ZrO₂, F, and transition metal oxides will comprise at least about 90% by weight of the glass-ceramic composition.

Glass-ceramic compositions within the above described composition range may be compounded and melted in accordance with conventional glass-making practice, and thereafter formed into glass articles by conventional means such as pressing, rolling, casting, spinning or the like. The batch materials may consist of oxides or may comprise any other compounds which will decompose at melting temperatures to yield molten batches having calculated oxide compositions within the aforementioned range. For these compositions, melting typically requires temperatures in the range of about 1600°-1650° C. for times in the range of about 6-16 hours.

Glass articles formed from the above compositions may be converted by crystallization in situ into semi-crystalline glass-ceramic articles according to processes conventional for beta-spodumene and beta-quartz-containing glass-ceramics. Such processes comprise exposure of the articles to temperatures in the range of about 700°-800° C. for times in the range of about 1-4hours to obtain nucleation of the glass, followed by exposure to temperatures in the range of about 800°-1200° C. for times in the range of about 1-8 hours to obtain crystallization of the glass.

Following crystallization, the semicrystalline glass-ceramic articles are subjected to further heat treatment under reducing conditions to promote the development of an exuded surface phase comprising active transition metal oxide compounds thereon. Exuded films formed in the described composition system include one or more crystalline compounds selected from the group consisting of Co₃ O₄,Mn₃ O₄, Fe₃ O₄, NiAl₂ O₄, CoAl₂ O₄, MnAl₂ O₄, FeAl₂ O₄, VAl₂ O₄ , CuCr₂ O₄, NiFe₂ O₄, CoFe₂ O₄, MnFe₂ O₄, CoTiO₃, MnTiO₃, FeTiO₃, Co₂ TiO₄ and CoMn₂ O₄. These may be found alone, in combination with each other, or in solid solution or combination with MgAl₂ O₄, VAlO₄, CuAl₂ O₄,CrAl₂ O₄, MnCr₂ O₄ and FeCr₂ O₄.

The film-producing heat treatments suitably comprise heating at temperatures in the range of about 500°-1000° C. in a reducing atmosphere. Preferred atmospheres include hydrogen and hydrogen-containing atmospheres such as forming gas (H₂, N₂). These atmospheres may contain additional constituents such as water vapor, CO, CO₂, Cl₂ or sulfur. Of course, other conventional reducing atmospheres such as hexane, methane, ammonia or the like may also be employed if desired. Typical treatment times range from at least about 1/2 hour up to about 10 hours or more. Longer treatment times may be employed, if desired, but long treatments are of no practical benefit and are commercially undesirable.

After sufficient growth of the transition metal oxide film has been attained in accordance with the above-described treatment, it may be desirable to further treat the article to modify the properties of the surface film for certain applications. Leaching is sometimes useful to remove residual glassy phases and/or to modify the porosity of the film. Supplemental oxidizing and/or reducing treatments may also be employed to modify the oxidation states of certain of the film constituents. The precise nature of the supplemental treatment employed, if any, will depend on the properties desired in the film and the nature of the use for which the article is intended.

Examples of thermally-crystallizable glass compositions suitable for forming beta-spodumene and beta-quartz glass-ceramics having exuded surface films containing transition metal oxide compounds according to the invention are set forth in Table I below. Compositions are given in parts by weight on the oxide basis as calculated from the batch. These compositions were batch melted in platinum crucibles at 1625° C. for 16 hours, and then poured into steel molds to form 4 inches × 4 inches × 1/2inches slabs and annealed at 650° C. Most of the compositions shown also include minor amounts of As₂ O₅ as a fining agent; however, the amount remaining in the glass after melting is negligible and is therefore not reported.

                                      TABLE I                                      __________________________________________________________________________     Composition                                                                           1    2    3    4    5    6    7    8                                    __________________________________________________________________________     SiO.sub.2                                                                             63.2%                                                                               60.9%                                                                               58.7%                                                                               61.2%                                                                               59.3%                                                                               71.7%                                                                               71.7%                                                                               71.7%                                Al.sub.2 O.sub.3                                                                      20.5 20.9 19.5 20.5 20.5 15.0 15.0 15.0                                 Li.sub.2 O                                                                            3.5  3.5  3.8  3.5  3.5  4.5  4.5  4.5                                  TiO.sub.2                                                                             4.8  4.8  4.9  4.8  4.8  5.5  5.5  5.5                                  ZrO.sub.2                                                                             --   --   --   0.1  0.1  --   --   --                                   MgO    1.7  1.7  --   1.7  1.7  --   --   --                                   ZnO    1.2  1.2  2.8  1.2  1.2  --   --   --                                   Na.sub.2 O                                                                            0.6  0.6  0.6  0.6  0.6  --   --   --                                   K.sub.2 O                                                                             0.3  0.3  0.3  0.2  0.2  --   --   --                                   P.sub.2 O.sub.5                                                                       1.2  1.2  2.6  1.2  1.2  --   --   --                                   B.sub.2 O.sub.3                                                                       0.4  0.4  --   --   --   --   --   5.0                                  F      0.1  0.1  0.1  --   --   --   --   --                                   Br     --   --   0.4  --   --   --   --   --                                   MnO.sub.2                                                                             --   --   0.4  --   --   --   --   0.6                                  Fe.sub.2 O.sub.3                                                                      1.6  3.0  4.0  3.0  3.0  --   1.3  --                                   CoO    --   --   0.9  0.6  2.4  2.6  --   2.7                                  Nb.sub.2 O.sub.5                                                                      --   --   --   --   --   3.5  --   --                                   __________________________________________________________________________

The thermally-crystallizable glass articles in Table I, produced as above described, are thereafter treated as set forth below in Table II in order to produce glass-ceramic articles having beta-spodumene and/or beta-quartz solid solutions as principal crystalline phases and exuded surface films containing transition metal oxide compounds. Table II reports the crystallizing heat treatments employed to convert each thermally-crystallizable glass article to the semi-crystalline state, the principal crystal phase present in the articles after ceramming, the reducing heat treatments employed to promote the growth of transition metal oxide compounds present in the exuded surface films, the appearance of the articles after the growth treatments, and the dominant properties of the exuded films. The principal crystalline phases listed are generally solid solutions rather than specific compounds. In instances where forming gas is used as the reducing atmosphere, a gas consisting of 8% H₂ and 92% N₂ by volume was employed. Typical film thicknesses over the range of growth treatments employed range about 0.1-2 microns.

                                      TABLE II                                     __________________________________________________________________________                        1         2          3           4                          __________________________________________________________________________     Nucleation Treatment                                                                        2 hours - 780° C.                                                                  2 hours - 780° C.                                                                  2 hours - 780° C.                                                                  2 hours - 780° C.         Crystallizaton                                                                              6 hours - 1080° C.                                                                 2 hours - 1100° C.                                                                 2 hours - 1100° C.                                                                 2 hours - 1100° C.        Treatment                                                                      Principal Crystal                                                                           β-spodumene, ana-                                                                    β-spodumene, ana-                                                                    β-spodumene, ana-                                                                    β-spodumene,                Phases       tase, MgAl.sub.2 O.sub.4                                                                  tase, MgAl.sub.2 O.sub.5                                                                  tase, ZrAl.sub.2 O.sub.4                                                                  anatase                          Film Growth Treatment                                                                       2 hours - 500° C.                                                                  2 hours - 500° C.                                                                  2 hours - 500° C.                                                                  2 hours - 500° C.                      H.sub.2    H.sub.2    H.sub.2    forming gas                      Surface Appearance                                                                          purple metallic                                                                           black      black metallic                                                                            grey black                       Exuded Crystal Phases                                                                       FeAl.sub.2 O.sub.4                                                                        Fe.sub.3 O.sub.4, FeAl.sub.2 O.sub.4,                                                     Fe.sub.3 O.sub.4, CoAl.sub.2 O.sub.4,                                                     CoAl.sub.2 O.sub.4,                                                            Fe.sub.3 O.sub.4                                                    Mn.sub.3 O.sub.4, MnFe.sub.2 O.sub.4        Surface Properties                                                                          magnetic - good                                                                           magnetic - good                                                                           magnetic - good                                                                           magnetic - good                               hysteresis loop                                                                           hysteresis loop                                                                           hysteresis loop                                                                           hysteresis loop                                  5          6          7          8                             __________________________________________________________________________     Nucleation Treatment                                                                        2 hours - 780°  C.                                                                 2 hours - 780° C.                                                                  2 hours - 780° C.                                                                  2 hours - 780° C.         Crystallizaton                                                                              2 hours - 1080° C.                                                                 2 hours - 1100° C.                                                                 2 hours - 1100° C.                                                                 2 hours - 1100° C.        Principal Crystal                                                                           β-spondumene,                                                                        β-spodumene,                                                                         β-spodumene,                                                                         β-spodumene,                                                              CoTiO.sub.3,                     Phases       anatase    CoTiO.sub.3, Co.sub.2 TiO.sub.4                                                           CoTiO.sub.3                                                                               Co.sub.2 TiO.sub.4               Film Growth Treatment                                                                       2 hours - 500° C.                                                                  2 hours - 500° C.                                                                  2 hours - 500° C.                                                                  2 hours - 500° C.                      forming gas                                                                               forming gas                                                                               forming gas                                                                               forming gas                      Surface Appearance                                                                          grey black black      black      black                            Exuded Crystal Phases                                                                       CoAl.sub.2 O.sub.4, Co.sub.3 O.sub.4,                                                     Co.sub.3 O.sub.4, Co.sub.2 TiO.sub.4,                                                     Fe.sub.3 O.sub.4, TiFe.sub.                                                               Co.sub.3 O.sub.4, Mn.sub.3                                                     O.sub.4, CoMn.sub.2                                                            O.sub.4,                                      Fe.sub.3 O.sub.4, CoFe.sub.2 O.sub.4                                                      CoTiO.sub.3           CoTiO.sub.3                      Surface Properties                                                                          magnetic - good                                                                           active catalyst                                                                           active catalyst                                                                           very active catalyst,                         hysteresis loop                                                                           C.sub.6 H.sub.8 oxidation                                                                 CO oxidation                                                                              CO oxidation, C.sub.6                                                          H.sub.8                                                             C.sub.6 H.sub.8 oxidation                                                                 oxidation                        __________________________________________________________________________

From the foregoing examples it is readily apparent that a broad range of aluminosilicate and lithium aluminosilicate glass-ceramic compositions containing transition metal additives may be treated according to the invention to provide exuded transition metal spinel films thereon having a variety of uses.

Compositions which are utilized for producing transition metal films having desirable magnetic and electrical properties are titania-nucleated lithium aluminosilicate compositions consisting essentially, in weight percent on the oxide basis as calculated from the batch, of about 58-64% SiO₂, 19-21% Al₂ O₃, 2-5% Li₂ O, 2-7% TiO₂, 0-1% ZrO₂, 3-7% total of TiO₂ + ZrO₂, 0-1% F, and 1-6% total of transition metal additives, essentially including iron, selected in the indicated proportion from the group consisting of 1-5% Fe₂ O₃, 0-5% MnO₂, 0-5% CoO and 0-3% NiO. Exuded transition metal films produced from articles of these compositions typically include one or more compounds of spinel structure selected from the group consisting of Co₃ O₄, Fe₃ O₄, Mn₃ O₄, MnAl₂ O₄, FeAl₂ O₄, CoAl₂ O₄, MnFe₂ O₄, NiFe₂ O₄, and CoFe₂ O₄, essentially including at least one iron compound. Example I of Table I represents the presently preferred composition for producing a film having particularly desirable magnetic properties according to the invention.

Compositions which are utilized for producing glass-ceramic articles having exuded transition metal oxide films demonstrating useful catalytic activity consist essentially, in weight percent on the oxide basis as calculated from the batch of about 68-74% SiO₂, 14-19% Al₂ O₃, 0-5% Li₂ O, 0-6% TiO₂, 0-3% ZrO₂, 5-9% total TiO₂ + ZrO₂, 0-5% B₂ O₃, 0-3% F, and 1-10% total of transition metal additives selected in the indicated proportion from the group consisting of 0-5% Fe₂ O₃, 0-5% CoO, 0-5% MnO₂, 0-2% CuO, 0-2% Cr₂ O₃, and 0-3% NiO. Exuded transition metal films produced on articles of these compositions typically contain one or more compounds selected from the group consisting of CoTiO₃, Co₂ TiO₄ CoMn₂ O₄, Co₃ O₄, Mn₃ O₄, CoFe₂ O₄, CoAl₂ O₄, MnTiO₃, and FeTiO₃. Example 8 of Table I represents the presently preferred composition for producing a catalytically-active oxide film in this system.

Types of glass-ceramic articles other than alumino-silicate and lithium aluminosilicate beta-quartz and beta-spodumene articles are also useful in providing exuded transition-metal-containing films according to the invention. Another useful composition area is found to include somewhat diverse silicate, aluminosilicate, and boroaluminate base compositions wherein manganese is a major constituent, comprising at least about 10% by weight of the compositions. The operative composition area includes compositions consisting essentially, in weight percent on the oxide basis, as calculated from the batch, of about 10-60% MnO₂, at least one oxide selected in the indicated proportion from the group consisting of 10-70% SiO₂, 13-43% Al₂ O₃,and 0-35% B₂ O₃, essentially including at least about 5% B₂ O₃ and 20% Al₂ O₃ , when SiO₂ is absent, not exceeding about 5% B₂ O₃ when Al₂ O₃ is absent, and not exeeding about 10% B₂ O₃ when both SiO₂ and Al ₂ O₃ are present, the sum total of MnO₂ + SiO₂ + Al₂ O₃ + B₂ O₃ comprising at least about 60% by weight of the composition, 0-30% Nb₂ O₅, 0-20% TiO₂, 0-5% Fe₂ O₃, 0-10% NiO, 0--3% Cr₂ O₃, 0-10% ZrO₂, 0-35% La₂ O₃, 0-10% Ta₂ O₅, 0-15% BaO, 0-10% SnO₂, 0-3% CoO, 0-4% ZnO and 0-10% K₂ O.

MInor amounts of other compounds may, of course, be included within these compositions as aids in melting, to modify properties and so forth, including, for example, Li₂ O, Na₂ O, WO₃, P₂ O₅, MgO, Cl, F, MnO₃, Cu₂ O, V₂ O₅, As₂ O₃, and Sb₂ O₃.

Glass-ceramic compositions within the aforementioned composition range may be melted according to conventional practice, typically at temperatures in the range of about 1500-1600° C. for times on the order of about 6-16 hours. The molten glasses may be formed into glass articles by conventional means such as pressing, rolling, casting, drawing or the like. Batch materials for these glasses may comprise oxides or other compounds which will decompose at melting temperatures to yield molten batches having oxide compositions within the aforementioned range.

Glass articles formed from the above compositions may be converted by crystallization in situ into glass-ceramic articles by heat treatment at temperatures in the range of about 600°-1200° C. for times in the range of about 4-24 hours. Useful crystallization treatments comprise a nucleation step wherein the article is heated at temperatures in the range of about 600°-800° C. for times on the order of 1-4 hours. Principal crystal phases in these composition systems include MnAl₂ O₄, Mn₃ O₄, Mn₂ Al₂ (SiO₄)₂ and MnSiO₃ depending somewhat on the composition of the MnO₂ -(B₂ O₃, Al₂ O₃, SiO₂) base glass.

Following crystallization, the growth of transition-metal-containing oxide films on the surface of these glass-ceramic articles is promoted using reducion heat treatments substantially the same as those above described for beta-spodumene and beta-quartz-containing articles. Such treatments typically comprise heating to temperatures in the range of about 500°-1000° C. in a reducing atmosphere, preferably an atmosphere comprising hydrogen or nitrogen-hydrogen forming gas, for treatment times in the range from about 1/2 hour up to about 10 hours, or more. Again, longer treatments may be employed if desired, but these are not deemed of practical benefit.

Transition-metal-containing exuded films which may form in this composition system include Mn₃ O₄, Fe₃ O₄, MnAl₂ O₄, NiAl₂ O₄, NiFe₂ O₄, MnFe₂ O₄, MnCr₂ O₄,MnNb₂ O₆ NiNb₂ O₆, Mn₂ Al₂ (SiO₄)₂, and Ti₂ Nb₁₀ O₂₉. The compounds in this system may be found either alone or in solid solution or combination with other crystalline species such as MnSiO₃ and ZrO₂. Residual glassy phases may also be present. Whereas the transition metal oxide films produced in these systems typically differ in composition from the interior of the article, it is possible that in certain cases the predominant surface compound is also one which predominates in the article as a whole. Nevertheless treatment according to the invention is effective to increase crystal formation in the surface layers of the article such that improved surface properties are obtained.

Examples of thermally-crystallizable glass compositions suitable for forming silicate, aluminosilicate, and boroaluminate glass-ceramics having exuded surface films containing transition metal oxide compounds according to the invention are set forth in Table III below. Compositions are given in parts by weight on the oxide basis as calculated from the batch. The compositions were batch melted in platinum crucibles at 1600° C. for about 6 hours, and then poured into steel molds to form 3/8 ×5 × 5 inch slabs and annealed at about 600° C. A few of the compositions additionally contained minor amounts of As₂ O₅ as a fining agent, but the amount remaining in the glass after melting is small and is therefore not reported.

                                      TABLE III                                    __________________________________________________________________________     Compositon                                                                             9    10   11   12   13   14   15   16                                  __________________________________________________________________________     MnO.sub.2                                                                               43.0%                                                                               31.8%                                                                               45.0%                                                                               60.0%                                                                               51.5%                                                                              21.0%                                                                                40.0%                                                                               30.0%                              B.sub.2 O.sub.3                                                                        --   --   30.0  5.0 --   --   --   --                                  Al.sub.2 O.sub.3                                                                       20.6 15.1 25.0 20.0 13.3 43.0 25.0 20.0                                SiO.sub.2                                                                              35.4 19.7 --   --   22.2 34.0 25.0 30.0                                La.sub.2 O.sub.3                                                                       --   33.5 --   --   --   --   --   --                                  Nb.sub.2 O.sub.5                                                                       --   --   --   --   13.0 --   --   --                                  Ta.sub.2 O.sub.5                                                                       --   --   --   --   --   5.0  --   --                                  TiO.sub.2                                                                              10.0 --   --   --   --   --   --   --                                  SnO.sub.2                                                                              --   --   --   --   --   --   --   10.0                                K.sub.2 O                                                                              --   --   --   --   --   --   --   10.0                                BaO     --   --   --   15.0 --   --   --   --                                  ZnO     --   --   --   --   --   2.0  --   --                                  Cr.sub.2 O.sub.3                                                                       --   --   --   --   --   1.0  --   --                                  Fe.sub.2 O.sub.3                                                                       --   --   --   --   --   3.0  --   --                                  CoO     --   --   --   --   --   1.0  --   --                                  NiO     --   --   --   --   --   3.0  10.0 --                                  __________________________________________________________________________

The thermally-crystallizable glass articles of Table III, produced as above described, are thereafter treated as set forth below in Table IV in order to produce glass-ceramic articles having exuded surface films containing transition metal oxide compounds. Table IV reports the crystallization heat treatments employed to obtain bulk crystallization in situ of the articles, the principal crystalline phases present in the articles after ceramming, the reducing heat treatments employed to promote the growth of transition metal spinel films on the articles, the transition metal spinels present in the exuded surface films, the appearance of the articles after growth treatment, and the dominant properties of the exuded films. Film dielectric constant (K') and loss tangent (tan δ) are reported where determined on individual samples. In instances where forming gas is reported as present in the reducing atmosphere, a gas consisting of 8% H₂ and 92% N₂ by volume was employed. Typical film thicknesses for these exuded films over the range of growth treatments employed range about 0.1-4 microns.

                                      TABLE IV                                     __________________________________________________________________________                       9          10        11          12                          __________________________________________________________________________     Nucleation Treatment                                                                        4 hours - 650° C.                                                                  4 hours - 650° C.                                                                  4 hours - 700° C.                                                                  4 hours - 650° C.         Crystallization                                                                             2 hours - 800° C.                                                                  4 hours - 800° C.                                                                  4 hours - 800° C.                                                                  2 hours - 1000° C.        Treatment    4 hours - 1000° C.                                                                 4 hours - 1000° C.                              Principal Crystal                                                                           MnSiO.sub.3,                                                                              MnSiO.sub.3           Mn.sub.3 O.sub.4                 Phases       Mn.sub.2 Al.sub.2 (SiO.sub.4).sub.2                               Film Growth  4 hours - 1000° C.                                                                 4 hours - 800° C.                                                                  2 hours - 500° C.                                                                  2 hours - 700° C.         Treatment     H.sub.2   forming gas                                                                               forming gas                                                                               forming gas                      Surface Appearance                                                                          liver color                                                                               liver color                                                                               brown      grey brown                       Exuded Crystal Phases                                                                       Mn.sub.3 O.sub.4, MnAl.sub.2 O.sub.4                                                      MnAl.sub.2 O.sub.4, Mn.sub.3 O.sub.4                                                      Mn.sub.3 O.sub.4, MnAl.sub.2 O.sub.4                                                      MnAl.sub.2 O.sub.4,                                                            Mn.sub.3 O.sub.4                 Surface Properties                                                                          ferromagnetic                                                                             ferromagnetic                                                                             ferromagnetic                                                                             ferromagnetic                                 K' = 15.5  K'  = 14.0 K' = 8.7   K' = 14.8                                     tanδ = 0.042                                                                        tanδ = 0.002                                                                        tanδ = 0.06                                                                         tanδ = 0.53                                13         14         15         16                            __________________________________________________________________________     Nucleation Treatment                                                                        4 hours - 650° C.                                                                  4 hours - 650° C.                                                                  4 hours - 780° C.                                                                  4 hours - 650° C.         Crystallization                                                                             2 hours - 1000° C                                                                  4 hours - 1000° C.                                                                 4 hours - 1000° C.                                                                 2 hours - 700° C.         Treatment                                                                      Principal Crystal       MnSiO.sub.3                                                                               MnAl.sub.2 O.sub.4                                                                        MnSiO.sub.3                      Phases                                                                         Film Growth  2 hours - 700° C. 2 hours - 800° C.                                         2 hours - 1000° C.                                                                 2 hours - 500° C.                    Treatment    forming gas                                                                               forming gas                                                                               forming gas                                                                               forming gas                      Surface Appearance                                                                          brown      black      black      brown grey                       Exuded Crystal                                                                              Mn.sub.2 Al.sub.2 (SiO.sub.4).sub.2,                                                      Mn.sub.3 O.sub.4, MnAl.sub.2 O.sub.4                                                      Mn.sub.3 O.sub.4, MnAl.sub.2 O.sub.4,                                                     Mn.sub.3 O.sub.4,                                                              MnAl.sub.2 O.sub.4               Phases       MnNb.sub.2 O.sub.6    NiAl.sub.2 O.sub.4                          Surface Properties                                                                          ferromagnetic                                                                             ferromagnetic;                                                                            ferromagnetic;                                                                            ferromagnetic                                            active catalyst                                                                           active catalyst                                                     (CO, C.sub.6 H.sub.8 oxida-                                                               (CO, C.sub.6 H.sub.8 oxida-                                         tion)      tion)                                                    K' = 14.8  K' = 12.4             K' = 12.0                                     tanδ = 0.038                                                                        tanδ = 0.016    tanδ = 0.01                __________________________________________________________________________

While the foregoing examples indicate that a broad range of manganese-containing compositions may be treated according to the invention to provide exuded crystalline films thereon, the best film properties are produced over a somewhat narrower range of composition. Among the aluminosilicate glass-ceramic compositions amenable to treatment according to the invention, those consisting essentially, in weight percent on the oxide basis as calculated from the batch, of about 19-40% SiO₂, 13-43% Al₂ O₃, and 15-50% MnO₂, optionally including 0-4% ZnO, 0-10% TiO₂, 0-10% ZrO₂, 0-10% SnO₂, 0-10% NiO, 0-5% Fe₂ O₃, and 0-30% Nb₂ O₅, are preferred. These compositions may provide exuded films containing at least one of Mn₃ O₄, Fe₃ O₄, MnAl₂ O₄, NiAl₂ O₄, MnFe₂ O₄, NiFe₂ O₄, MnNb₂ O₆, Mn₂ Al₂ (SiO₄).sub. 2 and Ti₂ Nb₁₀ O₂₉, many of which provide desirable electrical, magnetic and/or catalytic properties.

Preferred boroaluminate glass-ceramic compositions according to the invention are those consisting essentially, in weight percent on the oxide basis as calculated from the batch, of about 20-35% Al₂ O₃, 5-35% B₂ O₃, and 28-60% MnO₂, optionally including 0-15% BaO and 0-35% La₂ O₃.These compositions provide Mn₃ O₄ and/or MnAl₂ O₄ -containing films of good quality having desirable electrical properties.

From the foregoing description it is apparent that a large number of exuded transition metal oxide films may be provided on glass-ceramic base articles according to the invention to impart a variety of useful properties thereto. Thus articles having configurations suitable for use as magnetic memories, such as discs, may be conventionally formed, crystallized and provided with flat surfaces, and thereafter heat treated to exude magnetic transition metal oxide films thereon. Similarly glass-ceramic tubes, honeycombs, or the like may be formed, heat treated to exude catalytically-active films thereon, and incorporated into catalytic reactors to provide stable, durable active elements. Of course, these examples are merely illustrative of the numerous applications for glass-ceramic articles having integral exuded films which may be practiced within the scope of the present invention as defined by the appended claims. 

I claim:
 1. A method of providing a glass-ceramic article having an exuded surface film comprising at least one transition metal compound selected from the group consisting of Mn₃ O₄, Fe₃ O₄, Co₃ O₄, NiAl₂ O₄, CoAl₂ O₄, MnAl₂ D₄, 2O₄, ValO₄, NiFe₂ O₄, CoFe₂ O₄, MnFe₂ O₄, MnTiO₃, CoTiO₃, FeTiO₃, Co₂ TiO₄ and CoMn₂ O₄ on at least a portion of the surface thereof which comprises the steps of:a. compounding a batch for a glass composition consisting essentially, in weight percent on the oxide basis as calculated from the batch, of about 55-80% SiO₂, 14-35% Al₂ O₃, 0-5% Li₂ O, 0-7% TiO₂, 0-10% ZrO₂, 3-13% total of said TiO₂ + ZrO₂, 0-3% F, and 0.1-10% total of transition metal oxide additives containing one or more of the transition metals manganese, iron, cobalt, chromium, nickel and vanadium in a combination which will provide one or more of said Mn₃ O₄, Fe₃ O₄, Co₃ O₄, NiAl₂ O₄, CoAl₂ O₄, MnAl₂ O₄, FeAl₂ O₄, VAlO₄, NiFe₂ O₄, CoFe₂ O₄, MnFe₂ O₄, MnTiO₃, CoTiO₃, FeTiO₃, Co₂ TiO₄ and CoMn₂ O₄ transition metal compounds on the surface of said article, said additives being selected in the indicated proportions from the group consisting of 0-5% MnO₂, 0-5% Fe₂ O₃, 0-3% CoO, 0-2% Cr₂ O₃, 0-3% V₂ O₅ and 0-10% NiO, the foregoing constituents comprising at least about 90% by weight of said composition and said composition being capable of forming a principle crystal phase selected from the group consisting of beta-spodumene and beta-quartz solid solutions upon thermal crystallization thereof; b. melting said batch at a temperature in the range of about 1600°-1650° C. for a time in the range of about 6-16 hours to provide a molten glass; c. forming the molten glass into a glass article; d. exposing the glass article to a temperature in the range of about 700°-800° C. for a time in the range of about 1-4 hours to obtain nucleation of the glass; e. thereafter exposing the article to a temperature in the range of about 800°-1200° C. for a time in the range of about 1-8 hours to obtain crystallization of the glass by the formation of a principal crystal phase selected from the group consisting of beta-quartz and beta-spodumene solid solution therein; and f. exposing the article to a temperature in the range of about 500°-1000° C. in a reducing atmosphere for a time in the range of about 1/2-10 hours to develop said exuded surface film comprising said transition metal compounds thereon.
 2. A method in accordance with claim 1 wherein the reducing atmosphere is selected from the group consisting of hydrogen and forming gas.
 3. A method in accordance with claim 1 wherein:a. the batch is compounded to provide a glass composition consisting essentially, in weight percent on the oxide basis as calculated from the batch, of about 58-64% SiO₂, 19-21% Al₂ O₃, 2-5% Li₂ O, 2-7% TiO₂, 0-1% ZrO₂, 3-7% total of TiO₂ + ZrO₂, 0-1% F, and 1-6% total of transition metal oxide additives, essentially including iron, selected in the indicated proportions from the group consisting of 1-5% Fe₂ O₃, 0-5% MnO₂, 0-5% CoO and 0-3% NiO, and b. the exuded surface film comprises at least one transition metal compound, essentially including at least one compound of iron, selected from the group consisting of Co₃ O₄, Fe₃ O₄, Mn₃ O₄, MnAl₂ O₄, FeAl₂ O₄, CoAl₂ O₄, NiAl₂ O₄, MnFe₂ O₄, NiFe₂ O₄ and CoFe₂ O₄ and exhibits magnetic hysteresis.
 4. A method in accordance with claim 1 wherein:a. the batch is compounded to provide a glass composition consisting essentially, in weight percent on the oxide basis as calculated from the batch, of about 68-74% SiO₂, 14-19% Al₂ O₃, 0-5% Li₂ O, 0-6% TiO₂, 0-3% ZrO₂, 5-9% total of TiO₂ + ZrO₂, 0-5% B₂ O₃, 0-3% F, and 1-10% total of transition metal additives selected in the indicated proportion from the group consisting of 0-5% Fe₂ O₃, 0-5% CoO, 0-5% MnO, 0-2% Cr₂ O₃, and 0-3% NiO, and b. the exuded surface film comprises at least one transition metal compound selected from the group consisting of CoTiO₃, Co₂ TiO₄, CoMn₂ O₄, Co₃ O₄, Mn₃ O₄, Fe₃ O₄, CoFe₂ O₄, CoAl₂ O₄, MnTiO₃, and FeTiO₃ and exhibits catalytic activity for oxidation.
 5. A method of providing a glass-ceramic article having an exuded ferromagnetic surface film comprising at least one transition metal compound selected from the group consisting of Mn₃ O₄, Fe₃ O₄, MnAl₂ O₄, NiAl₂ O₄, NiFe₂ O₄, MnFe₂ O₄, MnCr₂ O₄, MnNb₂ O₆, NiNb₂ O₆, Ti₂ Nb₁₀ O₂₉, and Mn₂ Al₂ (SiO₄)₂ on at least a portion of the surface thereof which comprises the steps of:a. compounding a batch for a glass composition consisting essentially, in weight percent on the oxide basis as calculated from the batch, of about 10-60% MnO₂, at least one oxide selected in the indicated proportion from the group consisting of 10-70% SiO₂, 13-43% Al₂ O₃, and 0-35% B₂ O₃, essentially including at least about 5% B₂ O₃ and 20% Al₂ O₃ when SiO₂ is absent, not exceeding about 5% B₂ O₃ when Al₂ O₃ is absent, and not exceeding about 10% B₂ O₃ when both SiO₂ and Al₂ O₃ are present, at least about 60% total of MnO₂ + SiO₂ + Al₂ O₃ + B₂ O₃, 0-30% Nb₂ O₅, 0-35% La₂ O₃, 0-10% Ta₂ O₅ , 0-15% BaO, 0-10% SnO₂, 0-4% ZnO, 0-10% ZrO₂, 0-20% TiO₂, 0-5% Fe₂ O₃, 0-10% NiO, 0-3% Cr₂ O₃, 0-3% CoO and 0-10% K₂ O; b. melting the batch at a temperature in the range of about 1500°-1600° C. for a time in the range of about 6-16 hours; c. forming the molten glass into a glass article; d. exposing the glass to a temperature in the range of about 600°-1200° C. for a time in the range of about 4-24 hours to obtain crystallization of the glass; and e. exposing the crystallized glass to a temperature in the range of about 500°-1000° C. in a reducing atmosphere for a time in the range of about 1/2-10 hours to develop said exuded surface film comprising said transition metal compounds therein.
 6. A method in accordance with claim 5 wherein the reducing atmosphere is selected from the group consisting of hydrogen and forming gas.
 7. A method in accordance with claim 5 wherein:a. the batch is compounded to provide a glass consisting essentially, in weight percent on the oxide basis as calculated from the batch, of about 19-40% SiO₂, 13-43% Al₂ O₃, 15-50% MnO₂, 0-4% ZnO, 0-10% TiO₂, 0-10% ZrO₂, 0-10% SnO₂, 0-10% NiO, 0-5% Fe₂ O₃, and 0-3% Nb₂ O₅, and b. the exuded surface film comprises at least one transition metal compound selected from the group consisting of Mn₃ O₄, Fe₃ O₄, MnAl₂ O₄, NiAl₂ O₄, MnFe₂ O₄, NiFe₂ O₄, MnNb₂ O₆, NiNb₂ O₆, Ti₂ Nb₁₀ O₂₉ and Mn₂ Al₂ (SiO₄)₂.
 8. A method in accordance with claim 5 wherein:a. the batch is compounded to provide a glass consisting essentially, in weight percent on the oxide basis as calculated from the batch, of about 20-35% Al₂ O₃, 5-35% B₂ O₃, 28-60% MnO₂, 0-15% BaO and 0-35% La₂ O₃ ; and b. the exuded surface film comprises at least one transition metal compound selected from the group consisting of Mn₃ O₄, and MnAl₂ O₄. 